WO2018163650A1 - Composition d'agent d'attaque chimique et procédé de gravure - Google Patents

Composition d'agent d'attaque chimique et procédé de gravure Download PDF

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Publication number
WO2018163650A1
WO2018163650A1 PCT/JP2018/002522 JP2018002522W WO2018163650A1 WO 2018163650 A1 WO2018163650 A1 WO 2018163650A1 JP 2018002522 W JP2018002522 W JP 2018002522W WO 2018163650 A1 WO2018163650 A1 WO 2018163650A1
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Prior art keywords
etching
mass
solution composition
etching solution
component
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PCT/JP2018/002522
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English (en)
Japanese (ja)
Inventor
大輔 大宮
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株式会社Adeka
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Priority to KR1020197026496A priority Critical patent/KR102300540B1/ko
Priority to CN201880016111.8A priority patent/CN110383430B/zh
Publication of WO2018163650A1 publication Critical patent/WO2018163650A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30604—Chemical etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only

Definitions

  • the present invention relates to an etching solution composition and an etching method using the same. More specifically, the present invention relates to an etching solution composition used for etching an indium oxide-based layer and an etching method using the same.
  • Patent Document 1 discloses an etching solution composition for indium-tin oxide (hereinafter also referred to as “ITO”) containing ferric chloride and hydrochloric acid.
  • ITO indium-tin oxide
  • Patent Document 2 discloses an aqueous solution containing cupric ions, organic acids, halogen ions, azoles, and polyalkylene glycols, which are copper or copper alloy etchants. Has been.
  • an etching solution containing hydrogen chloride such as the etching solution composition disclosed in Patent Document 1 is used to collectively etch an ITO layer or a laminate composed of an ITO layer and a copper layer, a substrate or a peripheral member Discoloration of the substrate, roughening of the surface of the base material and the peripheral member, elution of metal components from the surface of the base material and the peripheral member, and poor linearity of the formed thin lines are likely to occur.
  • the present invention has been made to solve the above-mentioned problems, and the problem is that even if it does not contain hydrogen chloride, the narrowing width by etching is small, the linearity is good, and the desired width. It is an object of the present invention to provide an etching solution composition useful for etching an indium oxide-based layer, which can form a thin wire having the following. Moreover, the place made into the subject of this invention is providing the etching method using the said etching liquid composition.
  • an etching solution composition for etching an indium oxide-based layer comprising: (A) 0.01 to 15% by mass of hydrogen peroxide; (B) 1 to 40% by mass of sulfuric acid; C) Amide compound represented by the following general formula (1): 0.01 to 10% by mass; (D) Halide ion source (excluding fluoride ion source) 0.00001 to 0.1% by mass And (E) a fluoride ion source of 0.001 to 1 mass%; and an etching solution composition containing water is provided.
  • R 1 , R 2 , and R 3 are each independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or the number of carbon atoms. Represents an aryl group having 6 to 8 carbon atoms which may be substituted with 1 or 2 alkyl groups)
  • an etching method including a step of etching an indium oxide-based layer using the above-described etching solution composition.
  • INDUSTRIAL APPLICABILITY it is useful for etching an indium oxide-based layer that does not contain hydrogen chloride, has a narrow width by etching, has good linearity, and can form a thin line having a desired width.
  • An etching solution composition can be provided.
  • the etching method using the said etching liquid composition can be provided.
  • “Etching” in the present specification means a technique of plastic forming or surface processing utilizing a corrosive action such as chemicals.
  • Specific examples of the use of the etching solution composition of the present invention include a removing agent, a surface smoothing agent, a surface roughening agent, a pattern forming agent, and a cleaning solution for a component adhering to a trace amount on a substrate.
  • the etching solution composition of the present invention can be suitably used as a remover because the removal rate of the layer containing indium oxide is fast.
  • it can obtain a pattern with a desired shape such as a rectangle when it is used for forming a finely shaped pattern having a three-dimensional structure, it can also be suitably used as a pattern forming agent.
  • the “indium oxide-based layer” in this specification is not particularly limited as long as it is a layer containing indium oxide.
  • the “indium oxide-based layer” is a general term for a layer made of at least one selected from, for example, indium oxide, indium-tin oxide, and indium-zinc oxide.
  • metal-based layer in the present specification is not particularly limited as long as it is a layer made of metal.
  • Metal-based layer is selected from, for example, metal layers such as copper, nickel, titanium, chromium, silver, molybdenum, platinum, palladium, and metal alloys typified by CuNi, CuNiTi, NiCr, Ag—Pd—Cu, etc. It is a general term for the layer which consists of 1 or more types.
  • the indium oxide-based layer is a layer containing indium-tin oxide and the metal-based layer is a layer containing copper, a desired fine line can be formed with high accuracy and the etching rate is also high. Is preferable.
  • the etching solution composition of the present invention contains (A) hydrogen peroxide (hereinafter also referred to as “component (A)”).
  • component (A) hydrogen peroxide
  • the concentration of the component (A) in the etching solution composition is in the range of 0.01 to 15% by mass.
  • concentration of the component (A) is less than 0.01% by mass, the etching rate becomes too slow, and the productivity is significantly reduced.
  • concentration of the component (A) is more than 15% by mass, the etching rate becomes too fast and it becomes difficult to control the etching rate.
  • the concentration of the component (A) is preferably in the range of 0.1 to 12% by mass, more preferably in the range of 1 to 10% by mass.
  • the etching solution composition of the present invention contains (B) sulfuric acid (hereinafter also referred to as “component (B)”).
  • component (B) sulfuric acid
  • the concentration of the component (B) in the etching solution composition is in the range of 1 to 40% by mass. When the concentration of the component (B) is less than 1% by mass, the etching rate becomes too slow and productivity is lowered. On the other hand, when the concentration of the component (B) is more than 40% by mass, the etching rate becomes too high, and it becomes difficult to control the etching rate, or the member or resist around the object to be etched is deteriorated. May end up.
  • the concentration of component (B) is preferably in the range of 5 to 30% by mass, more preferably in the range of 10 to 25% by mass.
  • the etching solution composition of the present invention contains (C) an amide compound represented by the following general formula (1) (hereinafter also referred to as “component (C)”).
  • R 1 , R 2 , and R 3 are each independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or 1 or Represents an aryl group having 6 to 8 carbon atoms which may be substituted with 2 alkyl groups.
  • alkyl group having 1 to 8 carbon atoms examples include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, 2-hexyl, 3- Examples include hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl and the like.
  • alkenyl group having 2 to 8 carbon atoms examples include vinyl, 1-methylethenyl, 2-methylethenyl, propenyl, butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl and the like.
  • aryl group having 6 to 8 carbon atoms which may be substituted with an alkyl group having 1 or 2 carbon atoms include, for example, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,3 -Dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl and the like.
  • amide compound represented by the general formula (1) examples include formamide, acetamide, propionic acid amide, butyric acid amide, N, N, -dimethylformamide, N-methylformamide, N, N-diethylformamide, meta Examples include acrylamide, acrylamide, N-phenylformamide, benzamide, N-methylacetamide, N, N-dimethylacetamide, and the like.
  • formamide when formamide is used, the difference (deviation) between the width of the resist pattern and the width of the fine line formed by etching is smaller, and the linearity of the formed fine line is further improved. This is preferable.
  • the concentration of the component (C) in the etching solution composition is in the range of 0.01 to 10% by mass.
  • concentration of the component (C) is less than 0.01% by mass, the linearity of the fine line formed by etching is lowered.
  • concentration of the component (C) is more than 10% by mass, the etching rate becomes too slow, and the productivity is significantly reduced.
  • concentration of component (C) is preferably in the range of 0.05 to 5% by mass, more preferably in the range of 0.1 to 1% by mass.
  • the etching solution composition of the present invention contains (D) a halide ion supply source (excluding a fluoride ion supply source, hereinafter also referred to as “component (D)”).
  • component (D) a halide ion supply source (excluding a fluoride ion supply source, hereinafter also referred to as “component (D)”).
  • the concentration of the component (D) in the etching solution composition is in the range of 0.00001 to 0.1% by mass. When the concentration of component (D) is less than 0.00001 mass%, the blending effect of component (D) may not be obtained. On the other hand, even if the concentration of the component (D) exceeds 0.1% by mass, the blending effect of the component (D) does not improve any more.
  • the concentration of component (D) is more preferably in the range of 0.0001 to 0.01% by mass.
  • halide ions supplied from the halide ion source include chloride ions, bromide ions, iodide ions, and the like.
  • a halide ion supply source for example, a water-soluble salt containing halide ions can be used.
  • water-soluble salts containing halide ions include halide salts such as sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide and potassium iodide; ammonium chloride and the like. .
  • it is preferable to use a halide salt because etching can be performed at a better rate, and an alkali metal chloride salt is more preferable, and sodium chloride is particularly preferable.
  • the etching solution composition of the present invention contains (E) a fluoride ion supply source (hereinafter also referred to as “(E) component”).
  • the concentration of the component (E) in the etching solution composition is in the range of 0.001 to 1% by mass. When the concentration of the component (E) is less than 0.001% by mass, the blending effect of the component (E) may not be obtained. On the other hand, even if the concentration of the component (E) is more than 1% by mass, the blending effect of the component (E) is not further improved.
  • the concentration of component (E) is more preferably in the range of 0.005 to 0.8% by mass.
  • the fluoride ion supply source is not particularly limited as long as it generates fluoride ions in the etching solution composition.
  • fluoride ion supply sources include hydrofluoric acid, ammonium fluoride, acidic ammonium fluoride (monohydrogen difluoride), buffered hydrofluoric acid (mixture of hydrofluoric acid and ammonium fluoride), hydrofluoric acid, and the like.
  • an alkali metal fluoride salt When used as a fluoride ion supply source, the alkali metal may remain on the object to be etched after the etching process. For this reason, hydrofluoric acid, ammonium fluoride, acidic ammonium fluoride, and buffered hydrofluoric acid are preferably used as the fluoride ion supply source, and acidic ammonium fluoride is particularly preferably used.
  • the etching solution composition of the present invention contains water as an essential component other than the components (A), (B), (C), (D) and (E).
  • the etching solution composition of the present invention inhibits the effects of the present invention as a component other than the components (A), (B), (C), (D), (E), and water.
  • a well-known additive can be mix
  • additives include a stabilizer for an etching solution composition, a solubilizer for each component, an antifoaming agent, a pH adjusting agent, a specific gravity adjusting agent, a viscosity adjusting agent, a wettability improving agent, a chelating agent, an oxidizing agent, and a reducing agent. And surfactants.
  • the concentration of these additives is generally in the range of 0.001 to 50% by mass.
  • chelating agent examples include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, tetraethylenepentaminepentaacetic acid, pentaethylenehexamineoctacetic acid, nitrilotriacetic acid, and alkali metal (preferably sodium) salts thereof.
  • Aminocarboxylic acid-based chelating agents hydroxyethylidene diphosphonic acid, nitrilotrismethylenephosphonic acid, phosphonobutanetricarboxylic acid, and their alkali metal (preferably sodium) salts; phosphonic acid-based chelating agents; oxalic acid, malonic acid , Succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid, their anhydrides and their alkali metal (preferably sodium) salts such as divalent or higher carboxylic acids Acid compounds, It can be cited an anhydride or dianhydride carboxylic acid compound of divalent or more dehydrated. The concentration of these chelating agents is generally in the range of 0.01 to 40% by mass.
  • a reducing agent As an additive, it is preferable to use a reducing agent as an additive.
  • the reducing agent include copper chloride, ferrous chloride, copper powder, silver powder and the like.
  • the concentration of these reducing agents is generally in the range of 0.01 to 10% by mass.
  • the etching method of the present invention includes a step of etching an indium oxide-based layer using the above-described etching solution composition of the present invention. If the etching liquid composition of this invention is used, the laminated body which consists of an indium oxide type layer and a metal type layer can be etched collectively.
  • the indium oxide based layer constituting the laminate may be one layer or two or more layers.
  • the metal-based layer constituting the laminate may be one layer or two or more layers.
  • the metal-based layer may be disposed in the upper layer, the lower layer, or the upper layer and the lower layer. Furthermore, indium oxide-based layers and metal-based layers may be alternately stacked.
  • a method for etching the indium oxide-based layer or the laminated body of the indium oxide-based layer and the metal-based layer at a time is not particularly limited, and a general etching method may be employed.
  • an etching method such as a dip method, a spray method, or a spin method can be given.
  • the base material is dipped in an etching solution composition under appropriate etching conditions and then pulled up.
  • the Cu / ITO layer on the PET substrate can be etched together.
  • Etching conditions in the dip-type etching method are not particularly limited, and may be set arbitrarily according to the shape, film thickness, etc. of the substrate (object to be etched).
  • the etching temperature is preferably 10 to 60 ° C., more preferably 20 to 40 ° C.
  • the temperature of the etchant composition may increase due to reaction heat. For this reason, you may control temperature by a well-known means so that the temperature of an etching liquid composition may be maintained in said range as needed.
  • the etching time is not particularly limited as long as it is sufficient to complete the etching. For example, in the wiring manufacturing of an electronic circuit board, if the film thickness is about 5 to 500 nm, the etching may be performed for about 10 to 600 seconds in the above temperature range.
  • the etching solution composition is sprayed on the base material under appropriate conditions, so that Cu / The ITO layer can be etched.
  • Etching conditions in the spray-type etching method are not particularly limited, and may be set arbitrarily according to the shape and film thickness of the object to be etched.
  • the spraying conditions can be selected from the range of 0.01 to 1.0 MPa, preferably in the range of 0.02 to 0.5 MPa, and more preferably in the range of 0.05 to 0.2 MPa.
  • the etching temperature is preferably 10 to 60 ° C., more preferably 20 to 40 ° C.
  • the temperature of the etchant composition may increase due to reaction heat. For this reason, you may control temperature by a well-known means so that the temperature of an etching liquid composition may be maintained in said range as needed.
  • the etching time is not particularly limited as long as it is sufficient to complete the etching. For example, in the wiring manufacturing of an electronic circuit board, if the film thickness is about 5 to 500 nm, the etching may be performed in the above temperature range for about 5 to 600 seconds.
  • the etching solution composition of the present invention and the etching method using this etching solution composition are preferably used mainly for processing electrodes and wirings of liquid crystal displays, plasma displays, touch panels, organic EL, solar cells, lighting fixtures, etc. can do.
  • Etching liquid compositions (Examples 1 to 11) were obtained by using the amide compounds shown in Table 1 and mixing the components so that each component had the composition shown in Table 2. In addition, water was mix
  • Example 12 to 22 A resist pattern having a width of 30 ⁇ m and an opening of 30 ⁇ m was formed using a positive liquid resist on a substrate in which an ITO layer (15 nm) and a Cu layer (400 nm) were laminated in this order on a glass substrate.
  • the substrate on which the resist pattern was formed was cut into a length of 20 mm ⁇ width of 20 mm to obtain a test piece.
  • the obtained test pieces were subjected to a dip etching process with stirring at 35 ° C. for 1 minute using the etching solution compositions of Examples 1 to 11 to form fine wires.
  • a resist pattern having a width of 30 ⁇ m and an opening of 30 ⁇ m was formed using a positive liquid resist on a substrate in which an ITO layer (15 nm) and a Cu layer (400 nm) were laminated in this order on a glass substrate.
  • the substrate on which the resist pattern was formed was cut into a length of 20 mm ⁇ width of 20 mm to obtain a test piece.
  • the obtained test pieces were subjected to a dip etching process with stirring at 35 ° C. for 1 minute using the etching solution compositions of Comparative Examples 1 to 5 to form fine wires.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)
  • Weting (AREA)

Abstract

L'invention concerne une composition d'agent d'attaque chimique servant à graver des couches à base d'oxyde d'indium, ladite composition d'agent d'attaque chimique est exempte de chlorure d'hydrogène mais provoque cependant un faible amincissement de la largeur au moyen de la gravure. La composition d'agent d'attaque chimique présente une bonne linéarité et peut former un fil mince comportant une largeur souhaitée. La composition d'agent d'attaque chimique, qui doit être utilisée pour graver des couches à base d'oxyde d'indium, comprend : (A) 0,01 à 15 % en masse de peroxyde d'hydrogène ; (B) 1 à 40 % en masse d'acide sulfurique ; (C) 0,01 à 10 % en masse d'un composé amide représenté par la formule générale (1) [R1, R2 et R3 représentent l'hydrogène, un groupe alkyle ayant de 1 à 8 atomes de carbone, etc.] ; (D) 0,00001 à 0,1 % en masse d'une source d'ions halogénures (hors source d'ions fluorures) ; (E) 0,001 à 1 % en masse d'une source d'ions fluorures ; et de l'eau.
PCT/JP2018/002522 2017-03-10 2018-01-26 Composition d'agent d'attaque chimique et procédé de gravure WO2018163650A1 (fr)

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KR1020197026496A KR102300540B1 (ko) 2017-03-10 2018-01-26 에칭액 조성물 및 에칭 방법
CN201880016111.8A CN110383430B (zh) 2017-03-10 2018-01-26 蚀刻液组合物和蚀刻方法

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JP2017-046469 2017-03-10
JP2017046469A JP6746518B2 (ja) 2017-03-10 2017-03-10 エッチング液組成物及びエッチング方法

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